WO2003064348A2 - Utilisation de carbonate de calcium precipite (ccp) provenant de la purification de betterave sucriere en tant que matiere prime dans l'industrie ceramique - Google Patents

Utilisation de carbonate de calcium precipite (ccp) provenant de la purification de betterave sucriere en tant que matiere prime dans l'industrie ceramique Download PDF

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WO2003064348A2
WO2003064348A2 PCT/ES2002/000049 ES0200049W WO03064348A2 WO 2003064348 A2 WO2003064348 A2 WO 2003064348A2 ES 0200049 W ES0200049 W ES 0200049W WO 03064348 A2 WO03064348 A2 WO 03064348A2
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Prior art keywords
ccpa
calcium carbonate
porous ceramic
sugar
clay
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PCT/ES2002/000049
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English (en)
Spanish (es)
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WO2003064348A3 (fr
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Anselmo Acosta Echeverria
Manuel Ruiz Holst
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Azucarera Ebro, S.L. Sociedad Unipersonal
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Priority to BR0215591-5A priority Critical patent/BR0215591A/pt
Priority to PCT/ES2002/000049 priority patent/WO2003064348A2/fr
Priority to US10/503,558 priority patent/US20050218546A1/en
Priority to EP02710886A priority patent/EP1498399A2/fr
Publication of WO2003064348A2 publication Critical patent/WO2003064348A2/fr
Publication of WO2003064348A3 publication Critical patent/WO2003064348A3/fr

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Definitions

  • the invention relates, in general, to the use of precipitated calcium carbonate of sugar origin (CCPA) as a raw material in the ceramic industry, in particular, in the manufacture of porous ceramic products.
  • CCPA precipitated calcium carbonate of sugar origin
  • the CCPA improperly known as lime foams or carbonated sugar sludge, are the inorganic precipitates resulting from the purification of beet juices by liming and subsequent carbonation, in order to eliminate all those substances other than sugars. Its production is carried out from limestone (CaCO 3 ) whose mission is to provide the CaO and CO 2 necessary to carry out the process of purification of those unsweetened substances of the diffusion juice from beet, since the CaO formed is transformed into Ca (OH) 2 , which causes an increase in pH, favoring the coagulation of these substances.
  • limestone CaCO 3
  • the CO 2 precipitates the Ca (OH) 2 , and with it the non-sugar substances, being able to separate the juice on the one hand and the precipitate, which is the CCPA, on the other hand.
  • the generation of the CCPA takes place through the following series of reactions:
  • CCPA CaCO 3 + Q ⁇ CaO + CO 2 CaO + H 2 O ⁇ Ca (OH) 2 Ca (OH) 2 + CO 2 ⁇ CaCO 3 (CCPA)
  • the CCPA have a powdery appearance with grayish tones, and easily agglomerate forming lumps .
  • this material which is generated in huge quantities in the sugar industries, is used as filler material for gravel, debris, etc., and in some cases for the correction of soils with excessively clayey textures, or with acidic pH. .
  • the invention faces the problem of providing an alternative use to which It is currently carried out, with the CCPAs generated in the sugar industry.
  • the solution provided by this invention is based on the fact that, after the physical-chemical and mineralogical characterization of said CCPA, it has been shown that said CCPA can be used in the same fields of application as commercial calcium carbonates, except for those fields in which that color is the most important requirement, for example, in the porous ceramic industry.
  • calcium carbonate as a raw material in the porous ceramic industry exerts a double function since, on the one hand, it serves as a calcium contribution so that the clays, when melted, form a crystalline structure incorporating the calcium provided by the networks carbonate, generating calcium silicates, which give stiffness and resistance to the cooked piece, and, on the other hand, when decomposing, an amount of CO 2 is released whose mission is to create pores in the structure of the piece, so that the water and air can circulate through it without difficulty, thereby reducing moisture expansion problems, increasing frost resistance, etc.
  • calcium carbonate has to decompose thermally.
  • a solution such as that provided by this invention allows the development of a process for the manufacture of porous ceramic products comprising the use of said CCPA as raw material, taking advantage of its higher CO 2 content than the corresponding stoichiometric calcium carbonate and its lower decomposition temperature .
  • Figure 1 shows a diagram of X-ray diffraction (DRX) of a calcium carbonate of sugar origin (CCPA), compared to a DRX diagram of a commercial crushed calcium carbonate (GCC) used in the porous ceramic industry.
  • DRX X-ray diffraction
  • Figure 2 shows a diagram in which the percentage of mass loss versus temperature of a CCPA and a GCC is represented.
  • Figure 3 shows an X-ray diffractogram of a powder obtained in the pilot plant by mixing red clay and CCPA, in an approximate ratio of CCPA of 6% (see Example 2, section 2.2).
  • Figure 4 is a graph showing the drying curve as a function of the time of a paste obtained in pilot plant by adding water to a mixture of red clay and CCPA, in an approximate ratio of CCPA of 6% (see Example 2, section 2.2).
  • Figure 5 shows the result of the dilatometry test performed on a paste obtained in a pilot plant by adding water to a mixture of red clay and CCPA, in an approximate ratio of CCPA of 6% (see Example 2, section 2.2).
  • Figure 6 shows an X-ray diffractogram of a tile cooked at 950 ° C obtained from a mixture of red clay and CCPA, in an approximate ratio of CCPA of 6% (see Example 2, section 2.2).
  • the invention relates, in general, to the use of a precipitated calcium carbonate of sugar origin (CCPA) as a raw material in the porous ceramic industry.
  • CCPA precipitated calcium carbonate of sugar origin
  • CCPA is a known material, generated in the sugar industry, which mainly comprises calcium carbonate (in the form of calcite) and has a typical decomposition temperature of 770 ° C.
  • Example 1 the obtaining and characterization of a CCPA suitable for the implementation of the present invention is described.
  • a process for the manufacture of a porous ceramic product comprising the steps of preparing a dough, kneading, molding, drying and cooking, characterized in that said dough contains a CCPA.
  • Said paste containing CCPA constitutes an additional object of this invention.
  • the invention provides a process for the manufacture of a porous ceramic product, hereinafter the process of the invention, comprising: a) mixing a carbonaceous clay base material, a CCPA and water, to obtain a paste liable to be kneaded; b) kneading said paste capable of being kneaded obtained in step a); c) molding said kneaded paste in step b) in the desired conformation to obtain a molded material; and d) drying and baking said molded material to obtain a porous ceramic product.
  • Illustrative examples of ceramic products that can be obtained by the process of the invention include all kinds of porous ceramic pieces, for example, bricks, tiles, tiles, tiles, etc.
  • any clay-based material which is deficient in carbonates, and which is suitable for the type of porous ceramic product to be obtained, for example, clays.
  • Any carbonate-deficient clay useful for the manufacture of ceramic ceramic products can be used in the process of the invention.
  • the process of the invention begins by dosing and mixing the appropriate amounts of clay-based material and CCPA.
  • the amount of calcium carbonate (provided by the CCPA) that is mixed with the clay-based material is between 5 and 20% by weight with respect to the total of the mixture, indicating that said CCPA (whose content in calcium carbonate it is between 88 and 92%) it is really a raw material for the manufacture of the porous ceramic product.
  • the CCPA has a suitable particle size for carrying out the process of the invention, since normally all of the CCPA particles have a size equal to or less than 20 ⁇ m, of which 80% of the particles have a size equal to or less than 10 ⁇ m.
  • the appropriate amount of water is added in order to obtain a paste that can be kneaded, which is normally 20-25% on dry matter.
  • the resulting paste is molded into the desired conformation in order to obtain a "raw" molded product.
  • the molding can be carried out by any conventional method or technique, for example, by extrusion, pressing, etc. In a particular embodiment, when the ceramic product is a tile, the molding is performed by extrusion.
  • the "raw” molded product is dried and cooked at the appropriate temperature.
  • the "raw” molded product is placed in an oven and heated at a temperature between 900 ° C and 1000 ° C, for a period of time between 5 and 7 hours.
  • Ceramic products have been manufactured using said CCPA as a raw material together with carbonaceous clay-based materials (see Example 2) and have been its physical-chemical and mineralogical properties and characteristics were evaluated by means of the pertinent norms, observing that said CCPA is not only a useful material as raw material for the manufacture of porous ceramic products but also improves some properties and characteristics of the final product.
  • the comparison of said CCPA with other commercial calcium carbonates has shown that said CCPA is useful in the same fields of application as calcium carbonates, except for those in which color is the most important requirement.
  • a CCPA as raw material in the manufacture of porous ceramic products can result in energy savings during the manufacturing process of said porous ceramic products since their decomposition temperature is lower than that of natural calcium carbonates and, therefore, The availability of calcium to form calcium silicates is at a lower temperature.
  • organic matter in said CCPA typically between 6% and 11% by weight, contributes in some way to reducing the energy that is necessary to contribute to reach the decomposition temperature of the calcium carbonate present in said CCPA.
  • porous ceramic product obtainable by the aforementioned process constitutes an additional object of this invention.
  • CCPA CCPA generated in a sugar installation
  • a typical chemical composition of a CCPA such as that used in the realization of this Example, is shown in Table 1, where it is compared with that of a crushed calcium carbonate (GCC), of the type commonly used in brick making ( commercial product supplied by "Blancos y Carbonatos Rodenses SL) Table 1
  • GCC crushed calcium carbonate
  • Figure 1 shows the X-ray diffraction diagram of a CCPA (section 1.1) and of a GCC supplied by "Blancos y Carbatos Rodenses S. L., where it can be seen that both samples have practically the same X-ray diffractogram.
  • CCPA parameters may vary within a range. relatively broad, as shown in Table 2, which also indicates the specific value for each parameter considered of a CCPA sample used in this test
  • Color M ⁇ crocolor "Color difference measuring device with data station The value L * indicates the position on the axis of darkness / lightness or brightness, the value a *, the position on the axis red / green and the value b *, the position on the blue / yellow axis pH Glass electrode
  • thermogram of the CCPA Comparing the thermogram of the CCPA with that of GCC, it is clear that the CCPA is a matte Rial high in calcium carbonate. Additionally, it can be observed that, in the case of CCPA, the total decomposition of calcium carbonate occurs at approximately 770 ° C (in an inert atmosphere), while in the case of the GCC, it does not take place until 840 ° C approximately in the same conditions.
  • the clay-based material composed of clay minerals: kaolinite, illite and to a lesser extent smectite; indications of carbonate and an appreciable amount of quartz
  • CCPA whose characteristics have been described in Example 1
  • the plasticity of the mixture was measured from the paste to determine if it was a suitable sample to be extruded. The percentage of water that is added when kneading was also calculated. (Liquid limit of a soil by the Casagrande apparatus method, UNE 103103: 1994. Plastic limit of a soil, UNE 103104: 1993). The results obtained were the following:
  • both the dried pieces and the cooked pieces were subjected to scanning electron microscopy to determine the pore size of the pieces and the best or worst fusion of said pieces at each temperature
  • Some tiles were baked at 930 ° C and others at 970 ° C (five and a half hours in the oven), verifying that: i) all the pieces cooked at 970 ° C underwent load deformation (slight deformation suffered by the tiles in their wider part that causes it to close inwards, which does not fit well with each other), although in the case of the tiles obtained with the mixture of clay and CCPA, the deformation by load was slightly lower than the of the rest of the tiles manufactured without said mixture (it was determined by direct observation); and ii) all tiles obtained at 930 ° C did not undergo load deformation.

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Abstract

Le carbonate de calcium précipité (CCPA) provenant de la purification de betterave sucrière, peut être utilisé, par ses caractéristiques physico-chimiques et minéralogiques, comme matière prime dans l'industrie céramique, en particulier, dans la fabrication de produits céramiques poreux.
PCT/ES2002/000049 2002-01-31 2002-01-31 Utilisation de carbonate de calcium precipite (ccp) provenant de la purification de betterave sucriere en tant que matiere prime dans l'industrie ceramique WO2003064348A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR0215591-5A BR0215591A (pt) 2002-01-31 2002-01-31 Emprego do carbonato de cálcio precipitado de origem açucareira (ccpa) como matéria prima na indústria cerâmica
PCT/ES2002/000049 WO2003064348A2 (fr) 2002-01-31 2002-01-31 Utilisation de carbonate de calcium precipite (ccp) provenant de la purification de betterave sucriere en tant que matiere prime dans l'industrie ceramique
US10/503,558 US20050218546A1 (en) 2002-01-31 2002-01-31 Use of precipitated calcium carbonate (pcc) originating from sugar as a raw material in the ceramic industry
EP02710886A EP1498399A2 (fr) 2002-01-31 2002-01-31 Utilisation de carbonate de calcium precipite (ccp) provenant de la purification de betterave sucriere en tant que matiere prime dans l'industrie ceramique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/ES2002/000049 WO2003064348A2 (fr) 2002-01-31 2002-01-31 Utilisation de carbonate de calcium precipite (ccp) provenant de la purification de betterave sucriere en tant que matiere prime dans l'industrie ceramique

Publications (2)

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WO2003064348A2 true WO2003064348A2 (fr) 2003-08-07
WO2003064348A3 WO2003064348A3 (fr) 2004-04-01

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PCT/ES2002/000049 WO2003064348A2 (fr) 2002-01-31 2002-01-31 Utilisation de carbonate de calcium precipite (ccp) provenant de la purification de betterave sucriere en tant que matiere prime dans l'industrie ceramique

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Country Link
US (1) US20050218546A1 (fr)
EP (1) EP1498399A2 (fr)
BR (1) BR0215591A (fr)
WO (1) WO2003064348A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015114175A1 (fr) * 2014-01-28 2015-08-06 Neos Additives, S.L Composition céramique à faible densité, utilisation du produit obtenu à partir de celle-ci

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101890202B1 (ko) * 2016-01-25 2018-08-21 (주)인에코 기능성 이미지 타일 및 그 제조방법
CN110922107B (zh) * 2019-11-22 2021-02-26 武汉理工大学 一种彩色碳化硬化材料及其制备方法和用途
NL2026440B1 (nl) * 2020-09-10 2022-05-30 Koninklijke Mosa B V Werkwijze voor het vervaardigen van keramische tegels

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2302979A1 (fr) * 1975-03-06 1976-10-01 Tech Tuiles Briques Centre Procede et dispositif perfectionnes pour la fabrication de produits alveolaires a base d'argile
FR2336348A1 (fr) * 1975-12-22 1977-07-22 Armines Procede pour l'obtention d'anorthite synthetique
EP0031208A1 (fr) * 1979-12-24 1981-07-01 F.L. Smidth & Co. A/S Procédé de préparation d'un agrégat fritté
EP0082754A1 (fr) * 1981-12-23 1983-06-29 SOCIETE FRANCAISE DE CERAMIQUE Société dite: Procédé de fabrication d'un matériau à base de pseudo-wollastonite
WO1995007867A1 (fr) * 1993-09-16 1995-03-23 British Technology Group Limited Composition ceramique pour ceramiques fines

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1992916A (en) * 1931-08-17 1935-02-26 Johns Manville Permeable ceramic material and process of making the same
US5458680A (en) * 1992-05-01 1995-10-17 Ecc International, Inc. Method of producing aggregated composite pigments using organic silicon compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2302979A1 (fr) * 1975-03-06 1976-10-01 Tech Tuiles Briques Centre Procede et dispositif perfectionnes pour la fabrication de produits alveolaires a base d'argile
FR2336348A1 (fr) * 1975-12-22 1977-07-22 Armines Procede pour l'obtention d'anorthite synthetique
EP0031208A1 (fr) * 1979-12-24 1981-07-01 F.L. Smidth & Co. A/S Procédé de préparation d'un agrégat fritté
EP0082754A1 (fr) * 1981-12-23 1983-06-29 SOCIETE FRANCAISE DE CERAMIQUE Société dite: Procédé de fabrication d'un matériau à base de pseudo-wollastonite
WO1995007867A1 (fr) * 1993-09-16 1995-03-23 British Technology Group Limited Composition ceramique pour ceramiques fines

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015114175A1 (fr) * 2014-01-28 2015-08-06 Neos Additives, S.L Composition céramique à faible densité, utilisation du produit obtenu à partir de celle-ci

Also Published As

Publication number Publication date
EP1498399A2 (fr) 2005-01-19
WO2003064348A3 (fr) 2004-04-01
US20050218546A1 (en) 2005-10-06
BR0215591A (pt) 2004-12-21

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